Hair dye compositions

ABSTRACT

The present invention refers to hair dye compositions comprising one or more dyestuffs of the general formula (I) wherein R, X, Y and Z are defined as given in claim  1  and a process for colouring hair.

The present invention relates to hair dye compositions containinganthraquinone hair dyes.

Hair dyes can be classified by the dye to be used therefore, or bywhether they have bleaching action of melanin or not. Typical examplesinclude a two-part permanent hair dye composed of a first partcontaining an alkali agent, an oxidation dye and optionally a direct dyesuch as a nitro dye and a second part containing an oxidizing agent; anda one-part semi-permanent hair dye containing an organic acid or analkali agent, and an acid dye, basic dye or direct dye such as a nitrodye. The above-described permanent hair dye is however accompanied bythe drawback that the color tone imparted by an oxidation dye is not sovivid and that they damage the hair. Use of a nitro dye or cationic dyefor a two-component hair dye containing an oxidizing agent has beenattempted in order to produce various color tones (refer to, forexample, Japanese Patent Laid-Open No. 1994-271435 and EP 1 133 976 A2).A permanent hair dye formulation containing current direct dyestypically develop a vivid color just after dyeing, but the color fadesaway quickly over time and which leads to a dull end result. Also theuse of many direct dyes involves such problems as decomposition whenmixed with a peroxide serving as an oxidizing agent and incompatibilitywith the formulation.

The above described semi-permanent hair dye formulations are accompaniedby the drawback that the color imparted typically displays lowdurability. In addition, it is difficult to achieve violet, blue and ashtones since the number of dyes which can deliver these tones isextremely limited. Such dyes must be high performing and toxicologicallysafe.

It is known to use quaternized anthraquinone dyes to dye hairs, see forexample DE 1 203 915, DE 1 248 865, DE 1 492 066, GB 1 205 365, U.S.Pat. No. 3,531,502, EP 0 818 193 A2 and EP 0 852 136 A1. In addition,U.S. Pat. No. 3,657,213, GB 1,270,107, GB 1,248,652, U.S. Pat. No.2,888,467, U.S. Pat. No. 2,737,517, U.S. Pat. No. 4,246,172, CH14851/71, DE 16 19 365, CH 463666, FR 1,363,216, U.S. Pat. No. 5,486,629and GB 807241 teach to dye textile materials with quaternizedanthraquinone dyes.

However, there is still a need for hair dyes which can effectivelydeliver blue, ash, violet or red tones to the hair without damaging andare toxicologically safe.

It was now surprisingly found that specific anthraquinone dyes accordingto the definition given below provide the required properties.

Accordingly, the present invention provides hair dye compositionscomprising one or more dyestuffs of the general formula (I)

whereinR is hydrogen, alkyl, alkyl substituted by —OR²—, —SR³ or —NR⁵R⁴,hydroxyalkyl, polyhydroxyalkyl, cycloalkyl, aryl substituted by R¹⁰,R¹¹O-alkyl, —OR¹², —R¹³, —N¹⁴R¹⁵, —CONR¹⁵R¹⁶, —C(O)OR¹⁷, —SO₂—NR¹⁸R¹⁹,—SO₂OR²⁰, —C(O)R²¹ or —SO₂R²², —C(O)R⁶, —SO₂NR⁷R⁸ or —SO₂R⁹;X is hydrogen, —OR²³⁰, —SR²⁴⁰, —NR²⁵⁰R²⁶⁰, —SO₂NR²⁷⁰R²⁸⁰, —CONR²⁹⁰R³⁰⁰,—SO₂OR³¹⁰, —C(O)OR³²⁰, —C(O)R³³⁰, —SO₂R³⁴⁰, alkyl substituted by Q,—OR²⁰¹, —SR³⁰⁰ or —NR⁵⁰⁰R⁴⁰⁰, aryl substituted by R¹⁰⁰, R¹¹⁰O-alkyl,—OR¹²⁰, —SR¹³⁰, —NR¹⁴⁰R¹⁵⁰, —CONR¹⁵⁰OR¹⁶⁰, —C(O)OR¹⁷⁰, —SO₂—NR¹⁸⁰R¹⁹⁰,—SO₂OR²⁰⁰, —C(O)R²¹⁰ or —SO₂R²²⁰, —NHSO₂R³⁶⁰R³⁷⁰ or —CH═NR³⁵⁰;T is hydrogen, alkyl substituted by Q or aryl substituted by —OR²³⁰;Y is hydrogen, —NR⁵¹R⁵², —OR⁵³, —SR⁵⁴, —SO₂NHR⁵⁵, —NHC(O)R⁵⁶, —SO₂₀R⁵⁷,—NHSO₂R⁵⁸, —SO₂R⁵⁹, —NHSO₂NR⁶⁰R⁶¹, halogen or NO₂;Z is hydrogen, —NR⁵¹R⁵², —OR⁵³, —SR⁵⁴, —SO₂NHR⁵⁵, —NHC(O)R⁵⁶—SO₂OR⁵⁷,NHSO₂R⁵⁸, —SO₂R⁵⁹, —NHSO₂NR⁶⁰R⁶¹, halogen or NO₂;R¹ is hydrogen, —OH, —NH₂, —NHalkyl or NO₂;each of R² to R⁸, R⁶⁰ and R⁶¹, independently, is hydrogen, alkyl, aryl,hydroxyalkyl, polyhydroxyalkyl or cycloalkyl;R⁹ is alkyl, aryl, hydroxyalkyl, polyhydroxyalkyl or cycloalkyl;each of R¹⁰ to R²¹ independently, is hydrogen, alkyl, hydroxyalkyl,polyhydroxyalkyl or cycloalkyl;R²² is alkyl, hydroxyalkyl, polyhydroxyalkyl or cycloalkyl;each of R⁵¹ to R⁵⁴, independently, is hydrogen, alkyl, hydroxyalkyl,polyhydroxyalkyl, cycloalkyl, cycloalkyl substituted by —C(O)R⁶, —SO₂R⁹or aryl substituted by R¹⁰, R¹¹O-alkyl, —OR¹², —SR¹³, —NR¹⁴R¹⁵,—CONR¹⁵R¹⁶, —C(O)OR¹⁷, —SO₂—NR¹⁸R¹⁹, —SO₂OR²⁰, —C(O)R²¹ or —SO₂R²²;each of R⁵⁵ to R⁵⁷ independently, is hydrogen, alkyl, hydroxyalkyl,polyhydroxyalkyl, cycloalkyl or aryl substituted by R¹⁰, R¹¹O-alkyl,—OR¹², —SR¹³, —NR¹⁴R¹⁵, —CONR¹⁵R¹⁶, —C(O)OR¹⁷, —SO₂—NR¹⁸R¹⁹, —SO₂OR²⁰,—C(O)R²¹ or —SO₂R²²;each R⁵⁸ and R⁵⁹, independently, is alkyl, hydroxyalkyl,polyhydroxyalkyl, cycloalkyl or aryl substituted by R¹⁰, R¹¹O-alkyl,—OR¹², —SR¹³, —NR¹⁴R¹⁵, —CONR¹⁵R¹⁶, —C(O)OR¹⁷, —SO₂—NR¹⁸R¹⁹, —SO₂OR²⁰,—C(O)R²¹ or —SO₂R²²;each of R²³⁰, R²⁴⁰ and R³⁵⁰, independently, is alkyl substituted by Q,hydroxyalkyl substituted in the alkyl group by Q, polyhydroxyalkylsubstituted in the alkyl group by Q, cycloalkyl substituted by Q,—C(O)R⁶⁰⁰ or —SO₂R⁹⁰⁰, or aryl substituted by R¹⁰⁰, R¹¹⁰O-alkyl, —OR¹²⁰,—SR¹³⁰, —NR¹⁴⁰R¹⁵⁰, —CONR¹⁵⁰R¹⁶⁰, —C(O)OR¹⁷⁰, —SO₂—NR¹⁸⁰R¹⁹⁰, —SO₂OR²⁰⁰,—C(O)R²¹⁰ or —SO₂R²²⁰;each of R²⁰¹, R²⁰⁰, R⁶⁰⁰R⁹⁰⁰, independently, is alkyl substituted by Q,aryl substituted by Q, hydroxyalkyl substituted in the alkyl group by Q,polyhydroxyalkyl substituted in the alkyl group by Q, cycloalkylsubstituted by Q,each of R¹⁰⁰, R¹¹⁰, R¹²⁰, R¹³⁰, R¹⁷⁰, R²⁰⁰, R²¹⁰, R²²⁰, independently,is alkyl substituted by Q, hydroxyalkyl substituted in the alkyl groupby Q, polyhydroxyalkyl substituted in the alkyl group by Q, cycloalkylsubstituted by Q,each of R¹⁴⁰R¹⁵⁰R¹⁶⁰R¹⁸⁰ and R¹⁹⁰ is hydrogen, alkyl, alkyl substitutedby Q, hydroxyalkyl, hydroxyalkyl substituted in the alkyl group by Q,polyhydroxyalkyl, polyhydroxyalkyl substituted in the alkyl group by Q,cycloalkyl or cycloalkyl substituted by Q, with the proviso that eachthe groups —NR¹⁴⁰R¹⁵⁰, —CONR¹⁵⁰R¹⁶⁰ and —SO₂—NR¹⁸⁰R¹⁹⁰ must contain onegroup Q;is each of R³¹⁰, R³²⁰, R³³⁰ and R³⁴⁰ independently, is alkyl substitutedby Q, hydroxyalkyl substituted in the alkyl group by Q, polyhydroxyalkylsubstituted in the alkyl group by Q, cycloalkyl substituted by Q or arylsubstituted by R¹⁰⁰, R¹¹⁰O-alkyl, —OR¹²⁰, —SR¹³⁰, —N¹⁴⁰R¹⁵⁰,—CONR¹⁵⁰R¹⁶⁰, —C(O)OR¹⁷⁰, —SO₂—NR¹⁸⁰R¹⁹⁰, —SO₂OR²⁰⁰, —C(O)R²¹⁰ or—SO₂R²²⁰;each of R³⁶⁰ and R³⁷⁰ is hydrogen, alkyl, alkyl substituted by Q, aryl,aryl substituted by Q, hydroxyalkyl, hydroxyalkyl substituted in thealkyl group by Q, polyhydroxyalkyl, polyhydroxyalkyl substituted in thealkyl group by Q, cycloalkyl or cycloalkyl substituted by Q, with theproviso that the group —NHSO₂R³⁶⁰R³⁷⁰ must contain one group Q;each of R²⁵⁰R²⁶⁰R²⁷⁰R²⁸⁰R²⁹⁰ and R³⁰⁰, independently, is hydrogen,alkyl, alkyl substituted by Q, hydroxyalkyl, hydroxyalkyl substituted inthe alkyl group by Q, polyhydroxyalkyl, polyhydroxyalkyl substituted inthe alkyl group by Q, cycloalkyl or cycloalkyl substituted by Q,—C(O)R⁶⁰¹, —SO₂R⁹⁰¹, or aryl substituted by R¹⁰¹, R¹¹¹O-alkyl, —OR¹²¹,—SR¹³¹—NR¹⁴¹R¹⁵¹, —CONR¹⁵¹R¹⁶¹, —C(O)OR¹⁷¹, —SO₂—NR¹⁸¹R¹⁹¹, —SO₂OR²⁰²,—C(O)R²¹¹ or —SO₂R²²¹, with the proviso that each of the groups—NR²⁵⁰R²⁶⁰, —SO₂NR²⁷⁰R²⁸⁰ and —CONR²⁹⁰R³⁰⁰ must contain one group Q;each of R¹¹¹, R¹²¹, R¹³¹, R¹⁴¹, R¹⁵¹, R¹⁶¹, R¹⁷¹, R¹⁸¹, R¹⁹¹, R²⁰² andR²¹¹, independently, is hydrogen, alkyl, alkyl substituted by Q,hydroxyalkyl, hydroxyalkyl substituted in the alkyl group by Q,polyhydroxyalkyl, polyhydroxyalkyl substituted in the alkyl group by Q,cycloalkyl or cycloalkyl substituted by Q;R²²¹ is alkyl, alkyl substituted by Q, hydroxyalkyl, hydroxyalkylsubstituted in the alkyl group by Q, polyhydroxyalkyl, polyhydroxyalkylsubstituted in the alkyl group by Q, cycloalkyl or cycloalkylsubstituted by Q;R⁶⁰¹ is hydrogen, alkyl, alkyl substituted by Q, aryl, aryl substitutedby Q, hydroxyalkyl, hydroxyalkyl substituted in the alkyl group by Q,polyhydroxyalkyl, polyhydroxyalkyl substituted in the alkyl group by Q,cycloalkyl or cycloalkyl substituted by Q; andR⁹⁰¹ is alkyl, alkyl substituted by Q, aryl, aryl substituted by Q,hydroxyalkyl, hydroxyalkyl substituted in the alkyl group by Q,polyhydroxyalkyl, polyhydroxyalkyl substituted in the alkyl group by Q,cycloalkyl or cycloalkyl substituted by Q; andQ is a group of the general formula (II)

whereineach of R′, R″ and R′″, independently, is alkyl, aryl, arylalkyl,cycloalkyl, cycloalkylalkyl, heteroaryl, heteroarylalkyl,heterocycloalkyl, heterocycloalkyl-alkyl, either of which can besubstituted by heteroatom containing groups or R′ and R″ form togetherwith the nitrogen to which they are bonded a 5- or 6-memberedheterocyclic ring; andA⁻ is a cosmetically acceptable anion;whereby the dyestuff of the formula (I) contains exactly one group Q;whereby at least one of the groups Y and Z are groups other thanhydrogen; and whereby T and R¹ are hydrogen if X is different fromhydrogen.

Alkyl groups may be straight-chain or branched and are preferably(C₁-C₆)-alkyl groups, for example methyl, ethyl, n-propyl, isopropyl,n-butyl, n-pentyl, isopentyl or n-hexyl.

Cycloalkyl is preferably (C₃-C₈)-cycloalkyl and especially preferablycyclopentyl and cyclohexyl.

Aryl groups are preferably phenyl or naphthyl groups.

Halogen is preferably chlorine, bromine and fluorine.

A 5- or 6-membered heterocyclic ring which is formed by R′ and R″ ispreferably a pyrrolidine, piperidine, morpholine or piperazine ring. R′,R″ and R′″ are preferably benzyl or (C₁-C₆)-alkyl and especiallypreferably benzyl, methyl and ethyl.

The dyestuffs of the general formula (I) may be salts of an organic orinorganic acid. Consequently, A⁻ may be for example chloride, bromide,iodide, hydroxide, hydrogenphosphate, phosphate, carbonate,hydrogencarbonate, hydrogensulfate, perchlorate, fluoroborate,chlorozincate, methylsulfate, ethylsulfate, acetate, propionate, lactateor citrate or mixtures thereof.

The meaning of A⁻ is generally given by the preparation method of thedyestuff of the general formula (I). Preferred meanings of A⁻ arechloride, sulfate, hydrogensulfate, methylsulfate, ethylsulfate,phosphate, formate, acetate and lactate.

Especially preferred dye compositions of the present invention compriseone or more dyestuffs of the general formula (I) in which

Z, T and R¹ are hydrogen;R is hydrogen or (C₁-C₆)-alkyl;Y is —NR⁵¹R⁵², —NHSO₂R⁵⁸ or —OR⁵⁸, wherein R⁵¹ is hydrogen and R⁵² ishydrogen, (C₁-C₆)-alkyl, hydroxy-(C₁-C₆)-alkyl or phenyl; R⁵³ ishydrogen, (C₁-C₆)-alkyl or phenyl; and R⁵⁸ is (C₁-C₆)-alkyl or phenyl;X is —OR²³⁰ or —SR²⁴⁰, wherein R²³⁰ and R²⁴⁰ are (C₁-C₆)-alkylsubstituted by Q, phenyl substituted by Q, (C₁-C₆)-alkyl-SO₂-phenylwherein the alkyl group is substituted by Q or(C₁-C₆)-alkyl-NH—SO₂-phenyl, wherein the alkyl group is substituted byQ;Q is a tris-(C₁-C₆)-alkyl-ammonium group, abis(C₁-C₆)-alkyl-benzyl-ammonium group, a methyl-morpholinium group or amethyl-pyrrolidinium group; andA⁻ is chloride, sulfate, hydrogensulfate, methylsulfate, ethylsulfate,phosphate, formate, acetate or lactate.

Examples of dyestuffs of this type are the dyestuffs of the formulae(Ic), (Ig), (Ih), (Ii), (Ir), (Is), (Idd), (Iee and (Iff)

Further especially preferred dye compositions of the present inventioncomprise one or more dyestuffs of the general formula (I) in which

R is hydrogen or (C₁-C₆)-alkyl;Z, T and R¹ are hydrogen;Y is —NR⁵¹R⁵² or OR⁵³, wherein R⁵¹ and R⁵³ are hydrogen, R⁵² is(C₁-C₆)-alkyl, hydroxy-(C₁-C₆)-alkyl or phenyl;X is —SO₂NR²⁷⁰R²⁸⁰, —CONR²⁹⁰R³⁰⁰, —SO₂OR³¹⁰, —C(O)OR³²⁰, wherein R²⁷⁰and R²⁹⁰ are hydrogen or (C₁-C₆)-alkyl; R²⁸⁰, R³⁰⁰, R³¹⁰ and R³²⁰ are(C₁-C₆)-alkyl substituted by Q, hydroxy(C₁-C₆)-alkyl substituted in thealkyl group by Q or phenyl substituted by Q;Q is a tris(C₁-C₆)-alkyl-ammonium group, abis(C₁-C₆)-alkyl-benzyl-ammonium group, a methyl-morpholinium group or amethyl-pyrrolidinium group; andA⁻ is chloride, sulfate, hydrogensulfate, methylsulfate, ethylsulfate,phosphate, formate, acetate or lactate.

Examples of dyestuffs of this type are the dyestuffs of the formulae(Igg) to (Ijj):

Still further especially preferred dye compositions of the presentinvention comprise one or more dyestuffs of the general formula (I) inwhich

R is hydrogen or (C₁-C₆)-alkyl;T and R¹ are hydrogen;Z is —NR⁵¹R⁵² or —NHC(O)R⁵⁶, wherein R⁵¹ is hydrogen and R⁵² is hydrogenor (C₁-C₆)-alkyl and R⁵⁶ is (C₁-C₆)-alkyl or phenyl;Y is —NR⁵¹R⁵², wherein R⁵¹ is hydrogen, R⁵² is (C₁-C₆)-alkyl,hydroxy-(C₁-C₆)-alkyl or phenyl;X is —OR²³⁰, —SO₂NR²⁷⁰R²⁸⁰ or —SO₂OR³¹⁰, wherein R²³⁰ and R³¹⁰ are(C₁-C₆)-alkyl substituted by Q, hydroxy(C₁-C₆)-alkyl substituted in thealkyl group by Q, phenyl substituted by Q; R²⁷⁰ is hydrogen, R²⁸⁰ is(C₁-C₆)-alkyl substituted by Q or hydroxy(C₁-C₆)-alkyl substituted inthe alkyl group by Q;Q is a tris(C₁-C₆)-alkyl-ammonium group, abis(C₁-C₆)-alkyl-benzyl-ammonium group, a methyl-morpholinium group or amethyl-pyrrolidinium group; andA⁻ is chloride, sulfate, hydrogensulfate, methylsulfate, ethylsulfate,phosphate, formate, acetate or lactate.

Examples of dyestuffs of this type are the dyestuffs of the formulae(Ix) and (Iy):

Still further especially preferred dye compositions of the presentinvention comprise one or more dyestuffs of the general formula (I) inwhich

Y, T and R¹ are hydrogen;R is hydrogen or (C₁-C₆)-alkyl;Z is —NR⁵¹R⁵² or —NHC(O)R⁵⁶, wherein R⁵¹ is hydrogen and R⁵² is hydrogenor (C₁-C₆)-alkyl and R⁵⁶ is (C₁-C₆)-alkyl or phenyl;X is —OR²³⁰, —SO₂NR²⁷⁰R²⁸⁰, —SO₂OR³¹⁰ or —NR²⁵⁰R²⁶⁰ wherein R²³⁰ andR³¹⁰ are (C₁-C₆)-alkyl substituted by Q, hydroxy-(C₁-C₆)-alkylsubstituted in the alkyl group by Q, or phenyl substituted by Q; R²⁷ ishydrogen, R²⁸ is (C₁-C₆)-alkyl substituted by Q or hydroxy-(C₁-C₆)-alkylsubstituted in the alkyl group by Q; R²⁵ is hydrogen and R²⁶ is(C₁-C₆)-alkyl substituted by Q;Q is a tris(C₁-C₆)-alkyl-ammonium group, abis(C₁-C₆)-alkyl-benzyl-ammonium group, a methyl-morpholinium group or amethyl-pyrrolidinium group which is bonded to X; andA⁻ is chloride, sulfate, hydrogensulfate, methylsulfate, ethylsulfate,phosphate, formate, acetate or lactate.

Examples of dyestuffs of this type are the dyestuffs of the formulae(Iz), (Iaa), (Ibb) and (Icc):

Still further especially preferred dye compositions of the presentinvention comprise one or more dyestuffs of the general formula (I) inwhich

R is hydrogen or (C₁-C₆)-alkyl;Z is —NR⁵¹R⁵² wherein R⁵¹ is hydrogen and R⁵² is hydrogen or(C₁-C₆)-alkyl;Y is OR⁵³, wherein R⁵³ is hydrogen;X is hydrogen,

R¹ is —NH₂ or —NH-alkyl;

T is alkyl substituted by Q or aryl substituted by —OR²³⁰; wherein R²³⁰is (C₁-C₆)-alkyl substituted by Q, hydroxy(C₁-C₆)-alkyl substituted inthe alkyl group by Q, —C(O)R⁶⁰⁰ or —SO₂R⁹⁰⁰ wherein R⁶⁰⁰ and R⁹⁰⁰ are(C₁-C₆)-alkyl substituted by Q or hydroxy(C₁-C₆)-alkyl substituted inthe alkyl group by Q;Q is a tris(C₁-C₆)-alkyl-ammonium group, abis(C₁-C₆)-alkyl-benzyl-ammonium group, a methyl-morpholinium group or amethyl-pyrrolidinium group; andA⁻ is chloride, sulfate, hydrogensulfate, methylsulfate, ethylsulfate,phosphate, formate, acetate or lactate.

Examples of dyestuffs of this type are the dyestuffs of the formulae(Ikk) to (Inn):

The dyestuffs of the formula (I) are partly known from for example U.S.Pat. No. 2,737,517, U.S. Pat. No. 2,888,467, CH 463666, FR 1,363,216 orDE 16 19 365.

Dyestuffs of the below defined formula (Ia), however, are still novel.

Accordingly, the present invention provides dyestuffs of the generalformula (Ia)

whereinR is hydrogen, alkyl, alkyl substituted by —OR², —SR³ or —NR⁵R⁴,hydroxyalkyl, polyhydroxyalkyl, cycloalkyl, aryl substituted by R¹⁰,R¹¹O-alkyl, —OR¹², —SR¹³, —NR¹⁴R¹⁵, —CONR¹⁵R¹⁶, —C(O)OR¹⁷—SO₂—NR¹⁸R¹⁹,—SO₂OR²⁰, —C(O)R²¹ or —SO₂R²², —C(O)R⁶, —SO₂NR⁷R⁸ or —SO₂R⁹;X is hydrogen, —OR²³⁵, —SO₂NR²⁷⁰R²⁸⁰ or —SO₂OR³¹⁰;Y is hydrogen, —NR⁵¹R⁵², —OR⁵³, —SR⁵⁴, —SO₂NHR⁵⁵, —NHC(O)R⁵⁶, —SO₂OR⁵⁷,—NHSO₂R⁵⁸, —SO₂R⁵⁹, —NHSO₂NR⁶⁰R⁶¹, halogen or NO₂;Z is hydrogen, —NR⁵¹R⁵², —OR⁵³, —SR⁵⁴, —SO₂NHR⁵⁵, —NHC(O)R⁵⁶, —SO₂OR⁵⁷,NHSO₂R⁵⁸, —SO₂R⁵⁹, —NHSO₂NR⁶⁰R⁶¹, halogen or NO₂;T is hydrogen or aryl substituted by —OR²³⁰;R¹ is hydrogen, —OH, —NH₂, —NHalkyl or NO₂;R²³⁵ is aryl substituted by —SO₂—NR¹⁸⁰R¹⁹⁰ or —SO₂R²²⁰;and Q, R² to R²², R⁵¹ to R⁶¹, R¹⁰⁰, R¹¹⁰, R¹²⁰, R¹³⁰, R¹⁴⁰, R¹⁵⁰, R¹⁶⁰,R¹⁷⁰, R¹⁸⁰, R¹⁹⁰, R²⁰⁰, R²¹⁰, R²²⁰, R²³⁰, R²⁷⁰, R²⁸⁰ and R³¹⁰ aredefined as given above.In preferred dyestuffs of the formula (Ia)Z is hydrogen or amino;R¹ is hydrogen or hydroxy;R is hydrogen;Y is hydroxy or amino; andX is —OR²³⁵, wherein R²³⁵ is (C₁-C₆)-alkyl-NH—SO₂-phenyl, wherein thealkyl group is substituted by Q; andT is hydrogen or aryl substituted by —OR²³⁰, wherein R²³⁰ is(C₁-C₆)-alkyl substituted by Q, hydroxy(C₁-C₆)-alkyl substituted in thealkyl group by Q, —C(O)R⁶⁰⁰ or —SO₂R⁹⁰⁰, wherein R⁶⁰⁰ and R⁹⁰⁰ are(C₁-C₆)-alkyl substituted by Q or hydroxy-(C₁-C₆)-alkyl substituted inthe alkyl group by Q.

Especially preferred dyestuffs of the formula (Ia) are the dyestuffs(Ii), (Is) and (Ikk) to (Inn).

The dyestuffs of the general formula (I) can be obtained by generallyknown methods, for instance via Ullmann type substitutions ofanthraquinone derivatives which contain exchangeable atoms or groupssuch as halogen, sulfonic acid group or nitro group by aliphatic amines,aromatic amines, alcohols, phenols, thiols, thiophenols and sulfurcontaining reagents. General procedures are described, for example, in“Ullmann's Encyclopedia of Industrial Chemistry”, VCHVerlagsgesellschaft, Weinheim 1985, volume A2, Anthraquinone Dyes andIntermediates, pages 357-412. The preparing reactions of the dyestuffscan be carried out in an organic solvent such as dimethylformamide,dimethylacetamide, halogenobenzenes etc., in water or preferably insurplus reagent. It is of advantage to carry out the reactions atelevated temperatures, preferably between 60° C. and 150° C.Acid-binding agents must be added or an excess of amine is used. Addingusual catalysts such as copper or copper salts or mixtures thereof canbe advantageously.

The alkoxyanthraquinones of the general formula (I) can be obtained viathe conversion of anthraquinonesulfonic acids by alcoholic alkali at50-130° C. The direct replacement of halogen to alkoxy- oraryloxyanthraquinones can be advantageously carried out with e.g.alcoholate or phenolate generated in situ with alkali or advantageouslywith metallic sodium. It is advantageously to carry out these reactionsunder water free conditions with dried reagents.

Preferred hair dye compositions according to the present inventioncomprise dyestuff mixtures comprising one or more dyestuffs of thegeneral formula (I) and one or more direct or oxidation dyestuff.

Examples of such direct dyes include dyes from the publicly availabledyestuff list issued by The European Cosmetic, Toiletry and PerfumeryAssociation (COLIPA) and especially Acid Yellow 1, Disperse Red 17,Basic Brown 17, Acid Black I, 4-Nitro-o-phenylenediamine, Picramic acid,HC Red 13, N,N-bis(2-hydroxyethyl)-2-nitro-p-phenylenediamine, HC Red 7,HC Blue 2, HC Yellow 4, HC Yellow 2, HC Orange 1, HC Red 1, HC Red3,4-Amino-3-nitrophenol, 2-Hydroxyethylamino-5-nitroanisole,3-Nitro-p-hydroxyethylaminophenol, 3-Methylamino-4-nitrophenoxytheanol,2-nitro-5-glyceryl methylaniline, HC Violet 1, HC Orange 2, HC Yellow9,4-Nitrophenylaminoethylurea, HC Red 10, HC Red 11, 2-Hydroxy-ethylpicramic acid, HC Blue 12, Hydroxyethyl-2-nitro-p-toluidine, HC Blue 11,HC Yellow 7, HC Yellow 10, 4-Amino-2-nitrophenylamine-2-carboxylic acid,2-Chloro-6-ethylamino-4-nitrophenol, HC Violet2,2-Amino-6-chloro-4-nitrophenol, 4-Hydroxpropylamino-3-nitrophenol, HCYellow 13, 2,6-Diamino-3-((pyridin-3-yl)azo)pyridine,N-(2-nitro-4-aminophenyl)-allylamine, Basic Violet 2, Basic Red 51,Basic Yellow 87, Basic Orange 31, Basic Red 76, Basic Brown 16, BasicYellow 57, Acid Orange 7, Acid Red 33, Acid Yellow 23, Acid Blue 9, AcidRed 92, Acid Yellow 3, Acid Violet 43, Disperse Violet 1, Acid Blue 62,Disperse Black 9, Hydroxyanthraquinoneaminopropylmethyl morpholiniummethosulfate, Lawsone, HC Blue 14, Curry Red, Acid Red 18, Acid Red 52,Acid Green 25, Disperse Blue 377, Pigment Red 57, HC Blue 15,Tetrabromophenol Blue, Basic Blue 7, Basic Blue 26, Basic Blue 99, BasicViolet 10, Basic Violet 14; cationic dyes as described in JapanesePatent Laid-Open Nos. 2204/1983, 118832/1997 and Japanese Laid-OpenPublications (PCT) Nos. 501322/1996 and 507545/1996 (please checknumbers); and methine type cationic dyes having a cyanine structure.

Preferred inventive hair dye compositions containing mixtures usuallycontain one or more dyestuffs of the general formula (I) in an amount 90to 10 wt. % and one or more direct or oxidation dyestuff in an amount of10 to 90 wt. % based on the total weight of the dyestuff mixture.

Preferably, they contain one or more dyestuffs of the general formula(I) in an amount 80 to 20 wt. % and one or more direct or oxidationdyestuff in an amount of 20 to 80 wt. % based on the total weight of thedyestuff mixture.

Especially preferably, the they contain one or more dyestuffs of thegeneral formula (I) in an amount 65 to 35 wt. % and one or more director oxidation dyestuff in an amount of 35 to 65 wt. % based on the totalweight of the dyestuff mixture.

Further preferred hair dye compositions according to the presentinvention contain the dyestuff of the general formulae (I) in amounts of0.0001 to 20 wt. %, preferably 0.001 to 20 wt. %, more preferably from0.01 to 10 wt. % and especially preferably from 0.05 to 5 wt. %, basedon the weight of the hair dye composition.

Hair dye compositions according to the present invention comprising adyestuff mixture as described above usually have a dyestuff contentbetween 0.001 to 20 wt. %, preferably from 0.01 to 20 wt. %, morepreferably from 0.05 to 10 wt. % and especially preferably from 0.1 to 5wt. %, based on the weight of the hair dye composition.

In the hair dye compositions according to the present invention, theinventive dyestuffs of the general formula (I) exhibit a high storagestability within a wide pH range from 2 to 11, which is a pH rangeordinarily employed for hair dyes, so that the hair dye composition ofthe present invention can be used at any pH in the above-described pHrange. Use in a pH range of from 2 or greater is however preferred fromthe viewpoint of dyeing property. Hair dye compositions of a pH range of2 to 8 and hair dye compositions of a pH range of 8 to 12 are preferred.

The desired pH value is usually adjusted using an alkali agent. Examplesof alkali agents include ammonia, alkanolamines such as monoethanolamineand isopropanolamine or salts thereof, guanidium salts such as guanidinecarbonate and hydroxides such as sodium hydroxide. The inventive hairdye compositions contain an alkali agent preferably in an amount of from0.01 to 20 wt. %, more preferably from 0.1 to 10 wt. %, especiallypreferably from 0.5 to 5 wt. % based on the total weight of thecomposition.

Since the dyestuffs of the formula (I) have high stability againstoxidizing agents, the inventive hair dye composition may also be appliedto hair together with an oxidizing agent. In other words, it can beprovided as a two-part composition composed of a first part containingthe dyestuff of the general formula (I) and a second part containing anoxidizing agent. In this case, hair dyeing and bleaching can be carriedout simultaneously, which facilitates more vivid hair dyeing.

Examples of oxidizing agent include hydrogen peroxide, persulfates suchas ammonium persulfate, potassium persulfate and sodium persulfate,perborates such as sodium perborate, percarbonates such as sodiumpercarbonate and bromates such as sodium bromate and potassium bromate.Hydrogen peroxide is especially preferred from the viewpoints of hairbleaching property, stability and effectiveness of the inventivedyestuffs of the general formula (I). Hydrogen peroxide may be used incombination with another oxidizing agent. The oxidizing agent ispreferably used in an amount of from 0.5 to 10 wt. %, especiallypreferably from 1 to 8 wt. %, based on the hair dye composition.

The first part containing the inventive dyestuff of the general formula(I) and the second part containing the oxidizing agent are mixed at avolume ratio preferably ranging from 2:1 to 1:3.

In the hair dye composition of the present invention, an oxidation dyecan be used in combination with the inventive dyestuff of the generalformula (I). Such combined use enables considerably vivid and intensedyeing which cannot be accomplished by the single use of the oxidationdye. For the oxidation dye, known developers and couplers ordinarilyemployed for an oxidation type hair dye can be used.

Examples of the developer include paraphenylenediamine,toluene-2,5-diamine, 2-chloro-paraphenylenediamine,N-methoxyethyl-paraphenylenediamine,N,N-bis(2-hydroxyethyl)-paraphenylenediamine,2-(2-hydroxyethyl)-paraphenylenediamine,2,6-dimethyl-para-phenylenediamine, 4,4′-diaminodiphenylamine,1,3-bis(N-(2-hydroxyethyl)-N-(4-aminophenyl)amino)-2-propanol,PEG-3,2,2′-paraphenylenediamine, paraaminophenol, paramethylaminophenol,3-methyl-4-aminophenol, 2-aminomethyl-4-aminophenol,2-(2-hydroxyethylaminomethyl)-4-aminophenol, orthoaminophenol,2-amino-5-methylphenol, 2-amino-6-methylphenol,2-amino-5-acetamidophenol, 3,4-diaminobenzoic acid, 5-aminosalicylicacid, 2,4,5,6-tetraaminopyrimidine, 2,5,6-triamino-4-hydroxypyrimidineand 4,5-diamino-1-(4′-chlorobenzyl)pyrazole and salts thereof.

Examples of the coupler include metaphenylenediamine,2,4-diaminophenoxyethanol, 2-amino-4-(2-hydroxyethylamino)anisole,2,4-diamino-5-methylphenetole, 2,4-diamino-5-(2-hydroxyethoxy)toluene,2,4-dimethoxy-1,3-diaminobenzene, 2,6-bis(2-hydroxyethylamino)toluene,2,4-diamino-5-fluorotoluene, 1,3-bis(2,4-diaminophenoxy)propane,metaminophenol, 2-methyl-5-aminophenol,2-methyl-5-(2-hydroxyethylamino)phenol, 2,4-dichloro-3-aminophenol,2-chloro-3-amino-6-methylphenol, 2-methyl-4-chloro-5-aminophenol,N-cyclopentyl-metaaminophenol,2-methyl-4-methoxy-5-(2-hydroxyethylamino)phenol,2-methyl-4-fluoro-5-aminophenol, resorcin, 2-methylresorcin,4-chlororesorcin, 1-naphthol, 1,5-dihydroxynaphthalene,1,7-dihydroxynaphthalene, 2,7-dihydroxynaphthalene,2-isopropyl-5-methylphenol, 4-hydroxyindole, 5-hydroxyindole,6-hydroxyindole, 7-hydroxyindole, 6-hydroxybenzomorpholine,3,4-methylenedioxyphenol, 2-bromo-4,5-methylenedioxyphenol,3,4-methylenedioxyaniline,1-(2-hydroxyethyl)amino-3,4-methylenedioxybenzene,2,6-dihydroxy-3,4-dimethylpyridine, 2,6-dimethoxy-3,5-diaminopyridine,2,3-diamino-6-methoxypyridine, 2-methylamino-3-amino-6-methoxypyridine,2-amino-3-hydroxypyridine, and 2,6-diaminopyridine and salts thereof.

As each of the developer and coupler, at least two of theabove-described developers or couplers are usable. The content of eachof them is preferably from 0.01 to 20 wt. %, especially preferably from0.05 to 10 wt. % based on the hair dye composition.

To the hair dye composition of the present invention, an autoxidationdye typified by an indole or an indoline, or a known direct dye such asa nitro dye or a disperse dye can also be added.

Addition of a polyol, polyol alkyl ether, cationic or amphoteric polymerand/or silicone to the hair dye composition of the present invention ispreferred, because the resulting composition can dye the hair uniformlyand provides improved cosmetic effects of the hair.

In addition to the above-described components, those ordinarily employedas a raw material for cosmetics can be added to the hair dye compositionof the present invention. Examples of such an optional component includehydrocarbons, animal or vegetable fats and oils, higher fatty acids,organic solvents, penetration promoters, cationic surfactants, naturalor synthetic polymers, higher alcohols, ethers, amphoteric surfactants,nonionic surfactants, anionic surfactants, protein derivatives, aminoacids, antiseptics, chelating agents, stabilizers, antioxidants, plantextracts, crude drug extracts, vitamins, colorants, perfumes andultraviolet absorbers.

The hair dye composition of the present invention can be prepared in aconventional manner to form a one-part composition or a two-partcomposition having a first part containing an alkali agent and a secondpart containing an oxidizing agent. The inventive dyestuff of thegeneral formula (I) may be incorporated in at least one of these partsof the two-part or three-part composition. When the hair dye compositionof the present invention is of the one-part type, it is applied to thehair directly, while when it is of the two- or three-part type, theseparts are mixed just before hair dyeing and the mixture is applied tothe hair.

In the case of preparation of a two-part type hair dye composition, thefirst part is typically prepared by mixing the Inventive dyestuff of thegeneral formula (I) and optionally an oxidation dye and adjusting the pHof the mixture to 8 to 12 with an alkali agent such as ammonia. Thesecond part is prepared by incorporating about 2 to 6 wt. % of hydrogenperoxide, adjusting the mixture to weakly acidic with phosphoric.

The hair dye composition of the present invention can be provided in theform of powder, transparent liquid, emulsion, cream, gel, paste,aerosol, aerosol foam or the like. It preferably has a viscosity of 2000to 100000 mPa·s upon its application to the hair (after mixing of allthe parts when the composition is a two-part or three-part type). Theabove-described viscosity is measured at 20° C. by using a Brookfieldrotary viscometer (No. 5 spindle, 5 rpm).

The present invention also refers to a process for colouring haircharacterized in that a hair dye composition as described above isapplied onto hair, left for 1 to 45 minutes and than rinsed off fromhair.

In a preferred inventive process the hair dye composition is mixed witha composition comprising at least one oxidizing agent.

In the following, embodiments of the invention are described in detailfor the purpose of illustrating only and not for the purpose of limitingthe same.

Preparation of Dyestuffs a) Preparation of([2-(1-amino-4-hydroxy-9,10-dioxo-9,10-dihydro-anthracen-2-ylsulfanyl)-ethyl]-trimethyl-ammoniummethylsulfate)

5.0 parts of sulfur, 14.0 parts of sodium sulfide hydrate are dissolvedin 80 parts of ethyl alcohol at 50-60° C. Thereafter 10 parts of1-amino-2-bromo-4-hydroxy-anthraquinone were added and the reactionmixture was kept for 5 hours under reflux. After cooling off andacidification with 100 parts of 2N HCl, the precipitate was filtered offand washed with water. Upon drying 14.3 parts of a red powder wereobtained. The isolated product was taken in 250 parts of 3% sodiumhydroxide solution, stirred for 20 minutes and filtered off. Thesulfur-free filtrate was treated further with 7.7 parts of2-dimethylaminoethyl chloride hydrochloride and the solution was heatedat reflux for 7 hours. After cooling off, the pH was adjusted to ca. 9.0with conc. HCl and the precipitate was filtered off, washed and dried togive 10.1 parts of product. For the quaternisation the isolated dye wasdispersed in 75 parts of chlorobenzene and treated with 3.3 parts ofdimethylsulfate. The mixture was stirred at 30° C. for 1 hour andthereafter for another hour at 40° C. After cooling at room temperaturethe precipitate was filtered off and washed with acetone. Upon drying11.7 parts of the dye of formula Ig were obtained. The reddish violetdye Ig is very good water-soluble. The analytic data are consistent withthe assigned structure for dye Ig.

Melting point: >204° C.;

λ_(max) (H₂O)=535 nm (9100).

b) Preparation of([2-(1,4-diamino-9,10-dioxo-9,10-dihydro-anthracen-2-yloxy)-ethyl]-trimethyl-ammoniummethylsulfate)

15 parts of 1,4-diamino-9,10-dioxo-9,10-dihydro-anthracene-2-sulfonicacid, 100 parts of 2-dimethylamino-ethanol and 15 parts of solid KOHwere heated together at 80° C. and kept at this temperature for 1 hour.After cooling off, mixture was poured into 500 parts of cold water. Theprecipitate was filtered off, washed with water and dried to yield areddish violet powder. 2.5 parts of the dyestuff thus obtained weredispersed in 50 parts of chlorobenzene and treated with 1.0 part ofdimethylsulfate. The reaction mixture was stirred at 40° C. for 3½hours. The precipitate was filtered off at 30° C. and washed withacetone. Upon drying 3.3 parts of the dye of formula Ih were obtained.The reddish violet dye 1 h is very good water-soluble. The analytic dataare consistent with the assigned structure for dye 1 h.

Melting point: >223° C.;

λ_(max) (H₂O)=533 nm (9200), 569 nm (9000).

c) Preparation of({3-[4-(1-amino-4-hydroxy-9,10-dioxo-9,10-dihydro-anthracen-2-yloxy)-benzenesulfonylamino]-propyl}-trimethyl-ammoniummethylsulfate)

30 parts of4-(1-amino-4-hydroxy-9,10-dioxo-9,10-dihydro-anthracen-2-yloxy)benzenesulfonylchloride were dispersed in 160 parts of acetonitrile. 20 parts of3-dimethylaminopropylamine were added dropwise. After stirring 4 hoursat room temperature, the reaction mixture was filtered off, washed withwater and dried to yield 35.0 parts of a dark red powder. 10.0 parts ofthe dye thus obtained were dispersed in 100 parts of chlorobenzene andtreated with 2.4 parts of dimethylsulfate. The reaction mixture wasstirred at 40° C. for 3 hours. The precipitate was filtered off andwashed with acetone. Upon drying 10.6 parts of the dye of the formula Iiwere obtained. The red dye Ii is very good water-soluble. The analyticdata are consistent with the assigned structure for dye Ii.

Melting point: >145° C.;

λ_(max) (H₂O)=521 nm (12200), 550 nm (shoulder, 9600).

d) Preparation of([2-(1-amino-4-methanesulfonylamino-9,10-dioxo-9,10-dihydro-anthracen-2-yloxy)-ethyl]-trimethyl-ammoniummethylsulfate)

5.7 parts ofN-[4-amino-3-(2-dimethylamino-ethoxy)-9,10-dioxo-9,10-dihydro-anthracen-1-yl]-methanesulfonamide,prepared from1-amino-4-methanesulfonylamino-9,10-dioxo-9,10-dihydro-anthracene-2-sulfonicacid, N,N-dimethylaminoethanolamine and potassium hydroxide at 60° C.,were dispersed in 50 parts of chlorobenzene and treated with 1.7 partsof dimethylsulfate. The reaction mixture was stirred at room temperaturefor 5 hours. The precipitate was filtered off and washed with acetone.Upon drying 5.8 parts of the dye of the formula Idd were obtained. Thered dye Idd is very good water-soluble. The analytic data are consistentwith the assigned structure for dye Idd.

Melting point: >206° C.;

λ_(max) (H₂O)=515 nm (9000).

e) Preparation of([2-(5-acetylamino-1-amino-9,10-dioxo-9,10-dihydro-anthracen-2-yloxy)-ethyl]-trimethyl-ammoniummethylsulfate)

5.5 parts ofN-[5-amino-6-(2-dimethylamino-ethoxy)-9,10-dioxo-9,10-dihydro-anthracen-1-yl]-acetamide,prepared from5-acetylamino-1-amino-9,10-dioxo-9,10-dihydro-anthracene-2-sulfonicacid, N,N-dimethylaminoethanolamine and potassium hydroxide at 60° C.,were dispersed in 75 parts of chlorobenzene and treated with 1.7 partsof dimethylsulfate. The reaction mixture was stirred at room temperaturefor 5 hours. The precipitate was filtered off and washed with acetone.Upon drying 4.8 parts of the dye of the formula Iz were obtained. Thered dye Iz is very good water-soluble. The analytic data are consistentwith the assigned structure for dye Iz.

Melting point: >280° C.;

λ_(max) (MeCN)=487 nm (18300).

Preparation of Hair Dye Compositions EXAMPLE A

The dyes listed in Table 1 below were dissolved into Base Formulation 1together with the compounds as follows:

Dyestuff of general formula (I) 0.5 g iso-Propanol 5.0 g AmmoniumHydroxide (25%) 5.0 g Water up to 100 g pH 10.2

EXAMPLE B

The dyes listed in Table 2 below were dissolved into Base Formulation 2together with the compounds as follows:

Dyestuff of general formula (I) 0.5 g iso-Propanol 5.0 g AmmoniumHydroxide (25%) 5.0 g Hydrogen Peroxide (50%) 6.0 g Water up to 100 g pH10.2

Dyeing Performance

a) Approximately 1.5 g of the Base Formulation I was applied to 1 g ofundamaged white goat hair at 30° C. for 30 mins. At the end of theprocessing time the tresses were rinsed with water, shampooed and thendried.

The color of the tresses was recorded by measuring L, a and b values ofthe tresses before and after the colouring using a hand held DatacolorMercury colour-measuring instrument and the value of delta E, which is aknown measure for the chroma, was calculated according to the well-knownequation: ΔE=(ΔL²+Δa²+Δb²)^(1/2) for each example (this will applyequally to every example hereinafter).

The results are shown in Table 1

TABLE 1 Dyestuff Color of Dyed Hair L a b Delta E Formula Ii PureMagenta 53.9 30.3 −5.7 45.0 Formula Ig Intense Violet 40.3 23.2 −13.954.7 Formula Ih Brilliant Purple 42.5 23.8 −20.8 57.7 Formula IddIntense Blue-Red 54 28.9 −0.52 41.8 Formula Ic Intense Purple 47.3 20.5−16 50.9

b) Approximately 1.5 g of the Base Formulation 2 was applied to 1 g ofundamaged white goat hair at 30° C. for 30 mins. At the end of theprocessing time the tresses were rinsed with water, shampooed and thendried. The color of the tresses was recorded as given in Example Aabove.

The results are shown in Table 2

TABLE 2 Dyestuff Color of Dyed Hair L a b Delta E Formula Ii PureMagenta 53.9 30.3 −5.7 45.0 Formula Ig Intense Violet 40.3 23.2 −13.954.7 Formula Ih Brilliant Purple 42.5 23.8 −20.8 57.7 Formula IddIntense Blue-Red 51.9 33.8 −0.63 46.6 Formula Ic Intense Purple 57.920.1 −11.6 39.5

1: A dye composition comprising one or more dyestuffs of formula (I)

wherein R is hydrogen, alkyl, alkyl substituted by —OR², —SR³ or —NR⁵R⁴,hydroxyalkyl, polyhydroxyalkyl, cycloalkyl, aryl substituted by R¹⁰,R¹¹O-alkyl, —OR¹², —SR¹³, —NR¹⁴R¹⁵, —CONR¹⁵R¹⁶, —C(O)OR¹⁷, —SO₂—NR¹⁸R¹⁹,—SO₂OR²⁰, —C(O)R²¹ or —SO₂R²², —C(O)R⁶, —SO₂NR⁷R⁸ or —SO₂R⁹; X ishydrogen, —OR²³⁰, —SR²⁴⁰, —NR²⁵⁰R²⁶⁰, —SO₂NR²⁷⁰R²⁸⁰, —CONR²⁹⁰R³⁰⁰,—SO₂OR³¹⁰, —C(O)OR³²⁰, —C(O)R³³⁰, —SO₂R³⁴⁰, alkyl substituted by Q,—OR²⁰¹, —SR³⁰⁰ or —NR⁵⁰⁰R⁴⁰⁰, aryl substituted by R¹⁰⁰, R¹¹⁰O-alkyl,—OR¹²⁰, —SR¹³⁰, —NR¹⁴⁰R¹⁵⁰, —CONR¹⁵⁰R¹⁶⁰, —C(O)OR¹⁷⁰, —SO₂—NR¹⁸⁰R¹⁹⁰,—SO₂OR²⁰⁰, —C(O)R²¹⁰ or —SO₂R²²⁰, —NHSO₂R³⁶⁰R³⁷⁰ or CH═NR³⁵⁰; T ishydrogen, alkyl substituted by Q or aryl substituted by —OR²³⁰; Y ishydrogen, —NR⁵¹R⁵², —OR⁵³, —SR⁵⁴, —SO₂NHR⁵⁵, —NHC(O)R⁵⁶, —SO₂OR⁵⁷,—NHSO₂R⁵⁸, —SO₂R⁵⁹, —NHSO₂NR⁶⁰R⁶¹, halogen or NO₂; Z is hydrogen,—NR⁵¹R⁵², —OR⁵³, —SR⁵⁴, —SO₂NHR⁵⁵, —NHC(O)R⁵⁶, —SO₂R⁵⁷, NHSO₂R⁵⁸,—SO₂R⁵⁹, —NHSO₂NR⁶⁰R⁶¹, halogen or NO₂; R¹ is hydrogen, —OH, —NH₂,—NHalkyl or NO₂; each of R² to R⁸, R⁶⁰ and R⁶¹, independently, ishydrogen, alkyl, aryl, hydroxyalkyl, polyhydroxyalkyl or cycloalkyl; R⁹is alkyl, aryl, hydroxyalkyl, polyhydroxyalkyl or cycloalkyl; each ofR¹⁰ to R²¹, independently, is hydrogen, alkyl, hydroxyalkyl,polyhydroxyalkyl or cycloalkyl; R²² is alkyl, hydroxyalkyl,polyhydroxyalkyl or cycloalkyl; each of R⁵¹ to R⁵⁴, independently, ishydrogen, alkyl, hydroxyalkyl, polyhydroxyalkyl, cycloalkyl, cycloalkylsubstituted by —C(O)R⁶, —SO₂R⁹, or aryl substituted by R¹⁰, R¹¹O-alkyl,—OR¹², —SR¹³, —NR¹⁴R¹⁵, —CONR¹⁵R¹⁶, —C(O)OR¹⁷, —SO₂—NR¹⁸R¹⁹, —SO₂OR²⁰,—C(O)R²¹ or —SO₂R²²; each of R⁵⁵ to R⁵⁷, independently, is hydrogen,alkyl, hydroxyalkyl, polyhydroxyalkyl, cycloalkyl or aryl substituted byR¹⁰, R¹¹O-alkyl, —OR¹², —SR¹³, —NR¹⁴R¹⁵, —CONR¹⁵R¹⁶, —C(O)OR¹⁷,—SO₂—NR¹⁸R¹⁹, —SO₂OR²⁰, —C(O)R²¹ or —SO₂R²²; each R⁵⁸ and R⁵⁹,independently, is alkyl, hydroxyalkyl, polyhydroxyalkyl, cycloalkyl oraryl substituted by R¹⁰, R¹¹O-alkyl, —OR¹², —SR¹³, —NR¹⁴R¹⁵, —CONR¹⁵R¹⁶,—C(O)OR¹⁷, —SO₂—NR¹⁸R¹⁹, —SO₂OR²⁰, —C(O)R²¹ or —SO₂R²²; each of R²³⁰,R²⁴⁰ and R³⁵⁰, independently, is alkyl substituted by Q, hydroxyalkylsubstituted in the alkyl group by Q, polyhydroxyalkyl substituted in thealkyl group by Q, cycloalkyl substituted by Q, —C(O)R⁶⁰⁰ or —SO₂R⁹⁰⁰, oraryl substituted by R¹⁰⁰, R¹¹⁰O-alkyl, —OR¹²⁰, —SR¹³⁰, —NR¹⁴⁰R¹⁵⁰,—CONR¹⁵⁰R¹⁶⁰, —C(O)OR¹⁷⁰, —SO₂—NR¹⁸⁰R¹⁹⁰, —SO₂OR²⁰⁰, —C(O)R²¹⁰ or—SO₂R²²⁰; each of R²⁰¹, R²⁰⁰, R⁶⁰⁰, R⁹⁰⁰, independently, is alkylsubstituted by Q, aryl substituted by Q, hydroxyalkyl substituted in thealkyl group by Q, polyhydroxyalkyl substituted in the alkyl group by Q,cycloalkyl substituted by Q, each of R¹⁰⁰, R¹¹⁰, R¹²⁰, R¹³⁰, R¹⁷⁰, R²⁰⁰,R²¹⁰, R²²⁰, independently, is alkyl substituted by Q, hydroxyalkylsubstituted in the alkyl group by Q, polyhydroxyalkyl substituted in thealkyl group by Q, cycloalkyl substituted by Q, each of R¹⁴⁰, R¹⁵⁰, R¹⁶⁰,R¹⁸⁰ and R¹⁹⁰ is hydrogen, alkyl, alkyl substituted by Q, hydroxyalkyl,hydroxyalkyl substituted in the alkyl group by Q, polyhydroxyalkyl,polyhydroxyalkyl substituted in the alkyl group by Q, cycloalkyl orcycloalkyl substituted by Q, with the proviso that each the groups—NR¹⁴⁰R¹⁵⁰, —CONR¹⁵⁰R¹⁶⁰ and —SO₂—NR¹⁸⁰R¹⁹⁰ must contain comprise onegroup Q; each of R³¹⁰, R³²⁰, R³³⁰ and R³⁴⁰, independently, is alkylsubstituted by Q, hydroxyalkyl substituted in the alkyl group by Q,polyhydroxyalkyl substituted in the alkyl group by Q, cycloalkylsubstituted by Q or aryl substituted by R¹⁰⁰, R¹¹⁰O-alkyl, —OR¹²⁰,—SR¹³⁰, —NR¹⁴⁰R¹⁵⁰, —CONR¹⁵⁰OR¹⁶⁰, —C(O)OR¹⁷⁰, —SO₂OR¹⁸⁰R¹⁹⁰, —SO₂OR²⁰⁰,—C(O)R210 or —SO₂R²²⁰; each of R³⁶⁰ and R³⁷⁰ is hydrogen, alkyl, alkylsubstituted by Q, aryl, aryl substituted by Q, hydroxyalkyl,hydroxyalkyl substituted in the alkyl group by Q, polyhydroxyalkyl,polyhydroxyalkyl substituted in the alkyl group by Q, cycloalkyl orcycloalkyl substituted by Q, with the proviso that the group—NHSO₂R³⁶⁰R³⁷⁰ must comprise one group Q; each of R²⁵⁰, R²⁶⁰, R²⁷⁰,R²⁸⁰, R²⁹⁰ and R³⁰⁰ independently, is hydrogen, alkyl, alkyl substitutedby Q, hydroxyalkyl, hydroxyalkyl substituted in the alkyl group by Q,polyhydroxyalkyl, polyhydroxyalkyl substituted in the alkyl group by Q,cycloalkyl or cycloalkyl substituted by Q.—C(O)R⁶⁰¹, —SO₂R⁹⁰¹, or arylsubstituted by R¹⁰¹, R¹¹¹O-alkyl, —OR¹²¹, —SR¹³¹, —NR¹⁴¹R¹⁵¹,—CONR¹⁵¹R¹⁶¹, —C(O)OR¹⁷¹, —SO₂—NR¹⁸¹R¹⁹¹, —SO₂OR²⁰², —C(O)R²¹¹ or—SO₂R²²¹, with the proviso that each of the groups —NR²⁵⁰R²⁶⁰,—SO₂NR²⁷⁰R²⁸⁰ and —CONR²⁹⁰R³⁰⁰ must comprise one group Q; each of R¹¹¹,R¹²¹, R¹³¹, R¹⁴¹, R¹⁵¹, R¹⁶¹, R¹⁷¹, R¹⁸¹, R¹⁹¹, R²⁰² and R²¹¹,independently, is hydrogen, alkyl, alkyl substituted by Q, hydroxyalkyl,hydroxyalkyl substituted in the alkyl group by Q, polyhydroxyalkyl,polyhydroxyalkyl substituted in the alkyl group by Q, cycloalkyl orcycloalkyl substituted by Q; R is alkyl, alkyl substituted by Q,hydroxyalkyl, hydroxyalkyl substituted in the alkyl group by Q,polyhydroxyalkyl, polyhydroxyalkyl substituted in the alkyl group by Q,cycloalkyl or cycloalkyl substituted by Q; R⁶⁰¹ is hydrogen, alkyl,alkyl substituted by Q, aryl, aryl substituted by Q, hydroxyalkyl,hydroxyalkyl substituted in the alkyl group by Q, polyhydroxyalkyl,polyhydroxyalkyl substituted in the alkyl group by Q, cycloalkyl orcycloalkyl substituted by Q; and R⁹⁰¹ is alkyl, alkyl substituted by Q,aryl, aryl substituted by Q, hydroxyalkyl, hydroxyalkyl substituted inthe alkyl group by Q, polyhydroxyalkyl, polyhydroxyalkyl substituted inthe alkyl group by Q, cycloalkyl or cycloalkyl substituted by Q; and Qis a group of formula (II)

wherein each of R′, R″, and R′″, independently, is alkyl, aryl,arylalkyl, cycloalkyl, cycloalkylalkyl, heteroaryl, heteroarylalkyl,heterocycloalkyl, heterocycloalkyl-alkyl, either of which can besubstituted by a heteroatom containing comprising groups or R′ and R″form together with the nitrogen to which they are bonded a 5- or6-membered heterocyclic ring; and A⁻ is a cosmetically acceptable anion;whereby the dyestuff of formula (I) comprises exactly one group Q;whereby at least one of the groups Y and Z are groups other thanhydrogen; and whereby T and R¹ are hydrogen if X is different fromhydrogen. 2: The dye composition according to claim 1, wherein in thegroup of formula (II) R′, R″, and R′″ are (C-1-C₆)-alkyl or benzyl andA⁻ is chloride, bromide, iodide, hydroxide, hydrogenphosphate,phosphate, carbonate, hydrogencarbonate, hydrogensulfate, perchlorate,fluoroborate, chlorozincate, methylsulfate, ethylsulfate, acetate,propionate, lactate or citrate or a mixture thereof. 3: The dyecomposition according to claim 1, wherein in formula (I) Z, T and R¹ arehydrogen; R is hydrogen or (C-₁-C₆)-alkyl; Y is —NR⁵¹R⁵², —NHSO₂R⁵⁸ or—OR⁵³, wherein R⁵¹ is hydrogen and R⁵² is hydrogen, (C₁-C₆)-alkyl,hydroxy-(C₁-C₆)-alkyl or phenyl; R⁵³ is hydrogen, (C₁-C₆)-alkyl orphenyl; and R⁵⁸ is (C₁-C₆)-alkyl or phenyl; X is —OR²³⁰ or —SR²⁴⁰,wherein R²³⁰ and R²⁴⁰ are (C₁-C₆)-alkyl substituted by Q, phenylsubstituted by Q, (C₁-C₆)-alkyl-SO₂-phenyl wherein the alkyl group issubstituted by Q or (C₁-C₆)-alkyl-NH—SO₂-phenyl, wherein the alkyl groupis substituted by Q; Q is a tris-(C₁-C₆)-alkyl-ammonium group, abis(C₁-C₆)-alkyl-benzyl-ammonium group, a methyl-morpholinium group or amethyl-pyrrolidinium group; and A⁻ is chloride, sulfate,hydrogensulfate, methylsulfate, ethylsulfate, phosphate, formate,acetate or lactate. 4: The dye composition according to claim 1, whereinin the general formula (I) R is hydrogen or (C₁-C₆)-alkyl; Z, T and R¹are hydrogen; Y is —NR⁵¹R⁵² or OR⁵³, wherein R⁵¹ and R⁵³ are hydrogen,R⁵² is (C₁-C₆)-alkyl, hydroxy-(C₁-C₆)-alkyl or phenyl; X is—SO₂NR²⁷⁰R²⁸⁰, —CONR²⁹⁰R³⁰⁰, —SO₂OR³¹⁰, —C(O)OR³²⁰, wherein R²⁷⁰ andR²⁹⁰ are hydrogen or (C₁-C₆)-alkyl; R²⁸⁰, R³⁰⁰, R³¹⁰ and R³²⁰ are(C₁-C₆)-alkyl substituted by Q, hydroxy(C₁-C₆)-alkyl substituted in thealkyl group by Q or phenyl substituted by Q; Q is atris(C₁-C₆)-alkyl-ammonium group, a bis(C₁-C₆)-alkyl-benzyl-ammoniumgroup, a methyl-morpholinium group or a methyl-pyrrolidinium group; andA⁻ is chloride, sulfate, hydrogensulfate, methylsulfate, ethylsulfate,phosphate, formate, acetate or lactate. 5: The dye composition accordingto claim 1, wherein in formula (I) R is hydrogen or (C₁-C₆)-alkyl; T andR¹ are hydrogen; Z is —NR⁵¹R⁵² or —NHC(O)R⁵⁶, wherein R⁵¹ is hydrogenand R⁵² is hydrogen or (C₁-C₆)-alkyl and R⁵⁶ is (C₁-C₆)-alkyl or phenyl;Y is —NR⁵¹R⁵², wherein R⁵¹ is hydrogen, R⁵² is (C₁-C₆)-alkyl,hydroxy-(C₁-C₆)-alkyl or phenyl; X is —OR²³⁰, —SO₂NR²⁷⁰OR²⁸⁰ or—SO₂OR³¹⁰, wherein R²³⁰ and R³¹⁰ are (C₁-C₆)-alkyl substituted by Q,hydroxy(C₁-C₆)-alkyl substituted in the alkyl group by Q, phenylsubstituted by Q; R²⁷⁰ is hydrogen, R²⁸⁰ is (C₁-C₆)-alkyl substituted byQ or hydroxy(C₁-C₆)-alkyl substituted in the alkyl group by Q; Q is atris(C₁-C₆)-alkyl-ammonium group, a bis(C₁-C₆)-alkyl-benzyl-ammoniumgroup, a methyl-morpholinium group or a methyl-pyrrolidinium group; andA⁻ is chloride, sulfate, hydrogensulfate, methylsulfate, ethylsulfate,phosphate, formate, acetate or lactate. 6: The dye composition accordingto claim 1, wherein in the general formula (I) Y, T and R¹ are hydrogen;R is hydrogen or (C₁-C₆)-alkyl; Z is —NR⁵¹R⁵² or —NHC(O)R⁵⁶, wherein R⁵¹is hydrogen and R⁵² is hydrogen or (C₁-C₆)-alkyl and R⁵⁶ is(C₁-C₆)-alkyl or phenyl; X is —OR²³⁰, —SO₂NR²⁷⁰R²⁸⁰, —SO₂OR³¹⁰ or—NR²⁵⁰R²⁶⁰, wherein R²³⁰ and R³¹⁰ are (C₁-C₆)-alkyl substituted by Q,hydroxy-(C₁-C₆)-alkyl substituted in the alkyl group by Q, or phenylsubstituted by Q; R²⁷ is hydrogen, R²⁸ is (C₁-C₆)-alkyl substituted by Qor hydroxy-(C₁-C₆)-alkyl substituted in the alkyl group by Q; R²⁵ ishydrogen and R²⁶ is (C₁-C₆)-alkyl substituted by Q; Q is atris(C₁-C₆)-alkyl-ammonium group, a bis(C₁-C₆)-alkyl-benzyl-ammoniumgroup, a methyl-morpholinium group or a methyl-pyrrolidinium group whichis bonded to X; and A⁻ is chloride, sulfate, hydrogensulfate,methylsulfate, ethylsulfate, phosphate, formate, acetate or lactate. 7:The dye composition according to claim 1, wherein in formula (I) R ishydrogen or (C₁-C₆)-alkyl; Z is —NR⁵¹R⁵² wherein R⁵¹ is hydrogen and R⁵²is hydrogen or (C₁-C₆)-alkyl; Y is OR⁵³, wherein R⁵³ is hydrogen; X ishydrogen, R¹ is —NH₂ or —NH-alkyl; T is alkyl substituted by Q or arylsubstituted by —OR²³⁰; wherein R²³⁰ is (C₁-C₆)-alkyl substituted by Q,hydroxy(C₁-C₆)-alkyl substituted in the alkyl group by Q, —C(O)R⁶⁰⁰ or—SO₂R⁹⁰⁰ wherein R⁶⁰⁰ and R⁹⁰⁰ are (C₁-C₆)-alkyl substituted by Q orhydroxy(C₁-C₆)-alkyl substituted in the alkyl group by Q; Q is atris(C₁-C₆)-alkyl-ammonium group, a bis(C₁-C₆)-alkyl-benzyl-ammoniumgroup, a methyl-morpholinium group or a methyl-pyrrolidinium group; andA⁻ is chloride, sulfate, hydrogensulfate, methylsulfate, ethylsulfate,phosphate, formate, acetate or lactate. 8: The dye composition accordingto claim 1, which further comprises at least one oxidative dyeprecursor, at least one coupling compound, or a combination thereof. 9:The dye composition according to claim 1, which further comprises anoxidizing agent. 10: The dye composition according to claim 1, which hasa pH value in the range of 2 to
 11. 11: A process for colouring haircomprising: (1) applying the hair dye composition according to claim 1onto hair for 1 to 45 minutes, and (2) rinsing off said hair dyecomposition from said hair. 12: A dyestuff of formula (Ia)

wherein R is hydrogen, alkyl, alkyl substituted by —OR², —SR³ or —NR⁵R⁴,hydroxyalkyl, polyhydroxyalkyl, cycloalkyl, aryl substituted by R¹⁰,R¹¹O-alkyl, —OR¹², —SR¹³, —NR¹⁴R¹⁵, —CONR¹⁵R¹⁶, —C(O)OR¹⁷, —SO₂—NR¹⁸R¹⁹,—SO₂OR²⁰, —C(O)R²¹ or —SO₂R²², —C(O)R⁶, —SO₂NR⁷R⁸ or —SO₂R⁹; X ishydrogen, —OR²³⁵, —SO₂NR²⁷⁰R²⁸⁰ or —SO₂OR³¹⁰; Y is hydrogen, —NR⁵¹R⁵²,—OR⁵³, —SR⁵⁴, —SO₂NHR⁵⁵, —NHC(O)R⁵⁶, —SO₂OR⁵⁷, —NHSO₂R⁵⁸, —SO₂R⁵⁹,—NHSO₂NR⁶⁰R⁶¹, halogen or NO₂; Z is hydrogen, —NR⁵¹R⁵², —OR⁵³, —SR⁵⁴,—SO₂NHR⁵³, —NHC(O)R⁵⁶, —SO₂OR⁵⁷, NHSO₂R⁵⁸, —SO₂R⁵⁹, —NHSO₂NR⁶⁰R⁶¹,halogen or NO₂; T is hydrogen or aryl substituted by —OR²³⁰; R¹ ishydrogen, —OH, —NH₂, —NHalkyl or NO₂; R²³⁵ is aryl substituted by—SO₂—NR¹⁸⁰R¹⁹⁰ or —SO₂R²²⁰; and Q, R² to R²², R⁵¹ to R⁶¹, R¹⁰⁰, R¹¹⁰,R¹²⁰, R¹³⁰, R¹⁴⁰, R¹⁵⁰, R¹⁶⁰, R¹⁷⁰, R¹⁸⁰, R¹⁹⁰, R²⁰⁰, R²¹⁰, R²²⁰, R²³⁰,R²⁷⁰, R²⁸⁰ and R³¹⁰ are defined as given in claim
 1. 13: The dyestuffaccording to claim 12, where Z is hydrogen or amino; R¹ is hydrogen orhydroxy; R is hydrogen; Y is hydroxy or amino; and X is —OR²³⁵, whereinR²³⁵ is (C₁-C₆)-alkyl-NH—SO₂-phenyl, wherein the alkyl group issubstituted by Q; and T is hydrogen or aryl substituted by —OR²³⁰,wherein R²³⁰ is (C₁-C₆)-alkyl substituted by Q, hydroxy(C₁-C₆)-alkylsubstituted in the alkyl group by Q, —C(O)R⁶⁰⁰ or —SO₂R⁹⁰⁰, wherein R⁶⁰⁰and R⁹⁰⁰ are (C₁-C₆)-alkyl substituted by Q or hydroxy-(C₁-C₆)-alkylsubstituted in the alkyl group by Q.